Di (alkenyl carbonate) esters of alkylidene bis-phenols



Patented Feb. 26, i952 nnammmzr. caanona'rm ESTERS or ALKYLIDENE BIS-PHENOLS James A. Bralley, Bristol, 1a.,m Frank B. Pope, Cuyahoga Falls, Ohio, assignors to The B. F. Goodrich Company, New York, N. Y., a corporation of New York No Drawing. Application March 19, 1947,

Serial No. 735,794

6 Claims. 1

' pounds, and pertains more specifically to certain unsaturated diesters which are capable of polymerization to form non-thermoplastic polymers, and to the polymers obtained by such polymerization.

It is well known that various unsaturated diesters may be polymerized to form polymers of high molecular weight which are industrially useful. However, all of the materials previously known sufler from a variety of disadvantages, one of the most important of which is the fact that a relatively large shrinkage in volume occurs during the polymerization reaction. This fact, of course, makes it impracticable to use such materials as molding resins of the thermosetting variety because of the impossibility of obtaining accurate dimensions in the finished product.

- We have now discovered a certain class of unsaturated diesters which possess the property of polymerizing readily, particularly in the presence of organic peroxide catalysts, to form hard, clear,

non-thermoplastic, resinous, solid materials, and which in addition change very little in volume during the polymerization process. The materials which possess these properties are certain esters of carbonic acid. More particularly, these materials are dicarbonate esters of alkylidene and alkylene bis-phenolsin which each of the hydroxy groups of the bis-phenol is esterifled with a carbonic acid group and the carbonic acid groups are further attached by their second valences to polymerizable alkenyl groups. That is, these materials are compounds having the general structure R-O-C0-ArAAr0-COR i 1'.

sented by Ar have each of their connecting valences on nuclear carbon atoms and preferably, although not necessarily, are arylene radi cals containing only discrete (i. e., not condensed) benzene rings and having their two connecting valences in para position to each other.

2 such as p-phenylene and hydrocarbon-substituted p-phenylene radicals, since such compounds are most easily prepared.

These diesters are prepared by a variety of methods; for example, a suitable alkenol may be reacted with phosgene to form the corresponding alkenyl chloroformate (or chlorocarbonate) as described by Schving et al., Bull. Soc. Chim. 43, 857-9 (1928). Two molecular proportions of the alkenyl chloroformate may then be reacted with the appropriate bis-phenol with the elimination of two molecular proportions of hydrogen chloride, to form the desired polyester as shown in the following equations:

0001; +1105 n-o-( -m 1101 2R--0CCl HO-Ar-A-Ar-H0 The diesters are also formed by reacting the phosgene with the desired bis-phenol to form the dichloroformate followed by reacting the product with two molecular proportions of the desired alkenol with the elimination of two molecular proportions of hydrogen chloride, as shown in the following equations:

HQ-Ar-A-Ar-OH 20001,

A third method comprises mixing together simultaneously all three reagents, the bis-phenol, the phosgene, and the alkenol in the proper molecular proportions.

All of these reactions involving phosgene and the ester of chloroformic acid are best carried out at moderate temperatures in order to avoid the formation of undesirable by-products, preferably at a temperature below about C., and more particularly at about 0 to 20 C. It is unnecessary to employ an excess of any of the reagents above the amount theoretically-necessary for the reaction, although such an excess is not harmful. Solvents which are relatively inert to the reactants such as acetone, ether, benzene, or the like, may be employed as the reaction medium, although in many cases no solvent at all is necessary. It has been found that the second in which the phosgene is reacted with the alkenol to form an alkenyl chloroformate, followed by reacting two molecular proportions of the chloroformate with the bis-phenol.

Among the alkenols which may be employed in such a process are the following: allyl alcohol, methyl vinyl carbinol, allyl carbinol, vinyl ethyl carbinol, methyl allyl carbinol, beta-allyl ethyl alcohol, beta-methyl allyl alcohol, beta-ethyl allyl alcohol, and the like all of which contain from 3 to 5 carbon atoms and have a methylene group attached by a double bond to a carbon atom. Of these, allyl alcohol and the beta-alkyl allyl alcohols, such as beta-methyl allyl alcohol, are preferred.

Any of the bis-phenols of the structure wherein Ar is an arylene hydrocarbon radical and A is a bivalent saturated aliphatic hydrocarbon radical, may be used to prepare the diesters of this invention. Examples of alkylidene bis phenols of this structure include bis-(i-hy a ketone, as is known to those skilled in the art. Other bis-phenols of the above structure which may also be used include 1,2-bis-4-hydroxyphenyl) ethane, 1,2 bis (2 hydroxyphenyl) ethane; 1,5-bis-(4-hydroxyphenyl) pentane; 1,3- bis-(4-hydroxyphenyl) -2,2-diethyl propane and their homologs.

The unsaturated esters of this invention may readily be polymerized by any of the methods commonly used for the polymerization of unsaturated organic materials. Any of the usual catalysts such as per-compounds, actinic light, etc., may be used to accelerate the polymerization process; Excellent results have been obtained by using as a catalyst an organic peroxide such as diacetyl peroxide, acetyl benzoyl peroxide, dibenzoyl peroxide, dicaprylyl peroxide, di-ochlorobenzoyl peroxide, ditoluyl peroxide, and the like. Although the polymerization may be -carpreierred, when the material is used as a molding compound, to carry out the polymerization merely by dissolving a suitable amount of catalyst- (from 0.05 to about 5% by i ht 01 more) in the monomeric polyester, placing the material in a mold, and allowing it to remain there until polymerization is complete. The reaction may be accelerated, of course, by heating the mixture moderately, that is. to a temperature below about 150 0., preferably to a temperature of 60 to 100 C. It may also be accelerated by the presence of small amounts of other polymerizable compounds such as di-acrylate esters and maleic anhydride. It has been found that the polymerization reaction tends to be inhibited by the presence of atmospheric oxygen, and for that reason it is preferred to carry out the polymerization in a closed container, from which substantially all of the atmospheric oxygen has been removed. Because of the extremely low shrinkage attendant upon the change from the monomeric to the polymeric condition of these polyesters, objects may be cast and molded very accurately to required dimensions. Moreover, the molded product is optically clear and free from strain and flaws.

The following specific examples are intended to illustrate more fully the nature or the invention, but are not to be construed as a limitation upon the scope thereof.

Example I To a mixture of 34 parts by weight of 2,2-bis- (4-hydroxyphenyl) propane, 37 parts of allyl chloroformate, and 40 parts of acetone, there was added slowly and with continuous stirring a solution of 13 parts of sodium hydroxide in 30 parts of water while the temperature of the reaction mixture was maintained at about 10 C. Stirring oi the reaction mixture was continued while the temperature was allowed to rise to about 25 C. The mixture was then washed several times with alkali and then with water to remove any unreacted bis-phenol and the sodium chloride; a small amount of acetone was then added to the product, and the mixture was heated to 150 C.

at less than 1 mm. pressure in order to remove all 01' the acetone and water. The product, 2,2- bis-(4-(allylcarbonato) phenyl) propane, oi. the formula CH: H

was a water white, viscous liquid having a refractive index at 20 C. of 1.5422 and a density of about 1.1 to 1.2.

Example II 57.1 parts by weight of 2,2-bis-(3-phenyl-4- hydroxyphenyl) propane were mixed with 37.1 parts of allyl chloroformate and the mixture dissolved in 40 parts of acetone. To this solution there was slowly added with stirring a solution of 12.8 parts of sodium hydroxide dissolved in 60 parts of water, while maintaining the temperature of the reaction mixture at about 5 to 10 C. Stirring of the reaction mixture was then continued for one hour while the temperature rose to about 25 C. The reaction mixture was then allowed to separate into a water layer and an oil layer; the oil layer was dissolved in ether, the ether solution washed repeatedly with alkali and then with water until free of alkali, dried over anried out in solution or in aqueous emulsion, it is hydrous sodium sulfate and the ether removed.

2,587,487 6 The product remaining, 2,2-bis-[3-phenyl-4-(altends to inhibit the polymerization of these malylcarbonato)-phenyll propane of the structure terials, it is generally desirable to carry out the CH: L tn. was a viscous oily liquid and was obtained in 88% polymerization in a closed vessel from which the yield. air has been removed by evacuation or by replacement with nitrogen or other inert gas. Any Example air dissolved in the monomeric material may be The procedure of Example I was repeated removed prior to polymerization by placing the using, in place of 2,2-bis-(4-hydroxyphenyl) promaterial in'a closed vessel and reducing the prespane, an equimolecular proportion of 1,5-bis-i4- sure therein. hydroxyphenyl) pentane (which may be pre- Although specific examples of the invention pared by condensing ,two moles of anisaldehyde have been herein described, it is not intended to with one mold of acetone; completely hydrogenlimit the invention solexy thereto, but to include ating the non-aromatic portion of the product all of the obvious variations and modifications and then demethylating the ether groups to the falling within the spirit and scope of the apbis-phenol). The product 1,5-bis-[4-ial1ylcarpended claims. bonato)-phenyl] pentane of the structure This application is a continuation-in-part of was a viscous oily liquid and was obtained in our copending application Serial No. 579,164 filed good yield. Feb. 21, 1945 now U. S. Patent No. 2,455,653.

In the manner specifically set forth in the ex- We claim: amples, the diallyl dicarbonate esters of the other 1. An unsaturated diester of the formula bis-phenols mentioned hereinabove are also pre- R c A .A A o. c .o R pared. Moreover, the corresponding dimethallyl II I esters and other dialkenyl esters of the class herein described are obtained when methallyl wherein R 15 an alkenyl radlcal contalmng from chloroformate and other alkenyl chloroformates 3 to 5 carbon atoms and having a methylene are used in place of allyl chloroformate. Such group attached by a double bond to a Carbon compounds are generally liquids or low melting tom. Ar is an arylen hydrocarbon radical solids, and, when in the pure form, are clear and i s h of i s con ctin valenc s on nuclear colorless. carbon atoms and being selected from the class As mentioned hereinabove, the monomeric unconsisting of p-phenylene and monophenyl-subsaturated diesters of this invention may be polystituted p-phenylene radicals and A is an alkylimerized by heating in the presence of any of the clone hydroc radical containing f om 1 t0 7 usual peroxide catalysts. For example, the 2,2- carbon atoms. bis-[4-(a1lylcarbonato phenyl] propane of Ex- 2. 2,2-bis-[4-(allylcarbonato) phenyll propane ample I was mixed with 2% by weight of benzoyl of the formula CH: H

peroxide and the mixture was heated for 24 hours 3. A polymer of the unsaturated diester defined at 75 C. The liquid monomer gelled to a fusiin claim 1. ble partially polymerized solid in 95 minutes, and 4. A polymer of the compound of claim 2. continued heating produced ahard,crystal-clear, 5. An ester of (A) an alkylidene-bis-phenol non-thermoplastic resin. The shrinkage of the wherein the alkylidene radical is a hydrocarbon material during polymerization was only 6.1% radical containing up to 5 carbon atoms, and (B) and the final product possessed a Barcol Impresan acid ester of carbonic acid and allyl alcohol; sor hardness of about 25. The refractive index of the polymer was 1.5662 and it possessed excelfled with (B). lent flexural strength. These properties render The p y of e ester of Claim 5- it unusually adaptable for use in casting of opti- JAMES A. BRALLEY. cal pieces, in low-pressure laminating and for FRANK B. POPE. various other purposes.

Other polyesters within the scope of this in- EFERENCES CITED vention may be polymerized by Similar methods The following references are of record in the file of this patent:

to give similar hard, non-thermoplastic resins using the same or other catalysts. It is also pos- UNITED STATES PATENTS sible to employ mixtures of two or more of these Number Name Date' polyesters with each other in such a polymeriza- 7 2,370,567 Muskat et a1 Feb, 27, 1945 tion, as well as mixtures of these polyesters with 2,370 571 Muskat r, 1 27 5 other polymerizable unsaturated compounds, as 2,379,250 Muskat et a1. June 26, 1945 well as with plasticizers, pigments, fillers, other 2,379,251 Muskat et a1. June 26, 1945 polymers or resins, dyes, etc. 2,384,115 Muskat et a1 Sept. 4, 1945 Because of the fact that atmospheric oxygen 2,385,932 Muskat et al. Oct. 2, 1945 wherein both hydroxy groups of (A) are esteri- 

1. AN UNSATURATED DIESTER OF THE FORMULA 